CN102324511B - Preparation method for lithium ion battery composite cathode material - Google Patents

Preparation method for lithium ion battery composite cathode material Download PDF

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CN102324511B
CN102324511B CN2011103034947A CN201110303494A CN102324511B CN 102324511 B CN102324511 B CN 102324511B CN 2011103034947 A CN2011103034947 A CN 2011103034947A CN 201110303494 A CN201110303494 A CN 201110303494A CN 102324511 B CN102324511 B CN 102324511B
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lithium ion
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赵海雷
杨茜
王捷
王静
王春梅
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University of Science and Technology Beijing USTB
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Abstract

The invention discloses a preparation method for a lithium ion battery composite cathode material, and belongs to the field of new materials and electrochemistry, and aims to provide a compound electrode material capable of charging and discharging at a high magnification and an economical and feasible preparation process. The preparation method comprises the following steps of: preparing Li4Ti5O12-TiO2 nano particles by using lithium acetate and tetrabutyl titanate as raw materials and ammonia water as a pH value regulator, and adopting a solvent thermal bonding treatment method; then uniformly coating a carbon source on the surface of the Li4Ti5O12-TiO2 composite particles through a rotary evaporation process; and performing high-temperature pyrolysis to prepare a Li4Ti5O12-TiO2/C composite material. The Li4Ti5O12-TiO2/C composite material prepared by the method is fine in particle and uniform in particle size and composition distribution, has high magnification property and cyclical stability, can bring advantages of Li4Ti5O12, TiO2 and C into play, is an ideal high-magnification lithium ion battery composite cathode material, and can be widely used in the fields of portable electronic equipment, electric vehicles, aerospace and the like.

Description

A kind of preparation method of composite cathode material for lithium ion cell
Technical field
The invention belongs to new material and electrochemical field, but be specifically related to a kind of Li of high power charging-discharging 4Ti 5O 12-TiO 2/ C composite cathode material for lithium ion cell and preparation method thereof.
Background technology
Under the dual-pressure of energy crisis and environmental pollution, each state is all striving to find novel energy, and the forerunner of green energy resource---lithium ion battery is widely used in the fields such as portable electric appts, Aero-Space, military affairs.At present, the electric automobile of the energy-conserving and environment-protective fashionable whole world makes the motive-power battery of height ratio capacity, high cyclical stability, high rate performance excellence become the emphasis of current research.
The graphite-like carbon negative pole material of commercial extensive use exists some drawbacks: the current potential of carbon electrode and the current potential of lithium metal are very near (100 mV vs. Li +/ Li), surface easily precipitating metal lithium forms dendrite, has potential safety hazard; Generate the SEI film with the electrolyte reaction in discharge process first, coulombic efficiency is low first; Lithium ion takes off in the embedding process repeatedly, and material structure is damaged and causes special capacity fade, has reduced its service life cycle.So Novel anode material has become the focus of current concern.
Li 4Ti 5O 12Have charge and discharge platform (1.55 V vs. Li stably +/ Li), and with electrolyte reaction, fail safe and coulombic efficiency is high first; In the removal lithium embedded process, changes in crystal structure is very little, is called as " zero strain material ", has good cyclical stability, long service life.Li 4Ti 5O 12Have huge using value as the power type negative material, cause its capacity attenuation when high current charge-discharge fast but conductivity is low, high rate performance is relatively poor.At present, improve Li 4Ti 5O 12The key of material power density is to improve its electronic conductivity and ionic conductivity, usually takes following methods:
(1) ion doping.In the Li position or the high-valence cationic doping is carried out in the Ti position, carry out low price in the O position anion doped, according to elrectroneutrality pcharge-neutrality principle, part Ti ion is by Ti 4+To Ti 3+Change, improve Li 4Ti 5O 12The electronic conductivity of material.But it improves Li 4Ti 5O 12The DeGrain of material high rate performance; Simultaneously, doped chemical enters Li 4Ti 5O 12Lattice can reduce the structural stability of material to a certain extent.The Wen Zhaoyin group of Shanghai silicate research institute is to Li 4Ti 5O 12Carry out the cation doping study on the modification, synthesized Li by solid phase method 3.95M 0.15Ti 4.9O 12(M=Al, Ga, Co) and Li 3.9Mg 0.1Al 0.15Ti 4.85O 12, Al is found in research 3+Doped with being beneficial to the specific capacity that improves material, its stable cycle performance; Doping Ga 3+Specific capacity for material slightly is improved, but cyclical stability reduces slightly; Co 3+And Mg 2+Doping has reduced Li to a certain extent 4Ti 5O 12The chemical property of material (Shahua Huang, Zhaoyin Wen, Xiujian Zhu, Zuxiang Lin. Effects of dopant on the electrochemical performance of Li 4Ti 5O 12As electrode material for lithium ion batteries. J. Power Sources 165 (2007) 408 – 412).
(2) introduce highly conductor phase, the method for usually taking carbon to coat.Carbon is dispersed in Li 4Ti 5O 12Particle surface has bridging action, has strengthened the electron conduction ability between particle, has improved the high rate performance of material.Simultaneously, carbon does not enter Li 4Ti 5O 12Lattice does not affect the structural stability of material.The Deng Zhenghua of the Chinese Academy of Sciences etc. are take PAALi as lithium source and carbon source, TiO 2For the titanium source having synthesized Li 4Ti 5O 12/ C negative material, particle size are about 200 nm, at 8.60 mA/cm 2Current density under discharge and recharge, specific capacity reaches 130.0 mAh/g first, cyclical stability good (Ziji Lin, Xuebu Hu, Yongjian Huai, Li Liu, Zhenghua Deng, Jishuan Suo. One-step synthesis of Li 4Ti 5O 12/ C anode material with high performance for lithiumion batteries. Solid State Ionics 181 (2010) 412 – 415).The Yu Zuolong of the Chinese Academy of Sciences etc. has synthesized Li by solid phase method 4Ti 5O 12/ GCNTs composite material, it has height ratio capacity and good high rate performance, under the current density of 10 C, discharge capacity reaches 143 mAh/g first, circulate after 100 times, specific capacity is 132 mAh/g(Xing Li, Meizhen Qu, Zuolong Yu. Preparation and electrochemical performance of Li 4Ti 5O 12/ graphitized carbon nanotubes composite. Solid State Ionics 181 (2010) 635 – 639).The Gao Lijun of CANADIAN SOLAR INC., has synthesized Li by sol-gel process 4Ti 5O 12/ C composite material, its high rate performance is good, stable cycle performance, when forming half-cell with lithium metal, under 60 C discharging conditions, specific capacity is 108.9 mAh/g first, and after 2000 circulations, capability retention is 75.9%, when forming lithium ion battery with spinel lithium manganate, 85% the when discharge capacity under 1 A/g current density is 60 mA/g (CN 101867036 A).The carbon coating type lithium titanate material of the preparations such as the Xu Nin of Tianjin Bamo Technology Co has good high rate performance, and during 10 C, reversible capacity is 150.1 mAh/g, the 90.3%(CN 101378119A of capacity when being 0.1 C).
(3) the preparation nano-scale particle, shorten the lithium ion the evolving path, improves the ionic conductivity of material.The Zhang Naiqing of Harbin Institute of Technology etc. has synthesized nanometer Li by sol-gel process 4Ti 5O 12Particle, particle size is about 100 nm, under 40 C current densities, the tool specific capacity is up to 108 mAh/g, and, material has excellent cyclical stability and capacity restoration (Naiqing Zhang, Zhimin Liu, Tongyong Yang, Chenglong Liao, Zhijun Wang, Kening Sun. Facile preparation of nanocrystalline Li 4Ti 5O 12And its high electrochemical performance as anode material for lithium-ion batteries. Electrochem. Commun. 13 (2011) 654 – 656).The Li that the Yang Li of Shanghai Communications University etc. synthesize by hydro thermal method 4Ti 5O 12Negative material, under the current density condition of 20 C, specific discharge capacity is 125 mAh/g, stable circulation, high-rate charge-discharge capability good (CN 101409341A).
TiO 2Theoretical specific capacity be 335 mAh/g, have suitable embedding lithium current potential (~ 2 V vs. Li +/ Li), cubical expansivity low (3 ~ 4%), be introduced into Li 4Ti 5O 12In, can improve the specific capacity of material.The alkaline molten salt growth methods of employing such as Australia M.M. Rahman have been synthesized nanometer Li 4Ti 5O 12-TiO 2Negative material, under 1 C current density condition, first discharge specific capacity is 146 mAh/g, circulate after 100 times, capability retention is 95%(M.M. Rahman, Jia-Zhao Wang, Mohd Faiz Hassan, Shulei Chou, David Wexler, Hua-Kun Liu. Basic molten salt process-A new route for synthesis of nanocrystalline Li 4Ti 5O 12-TiO 2Anode material for Li-ion batteries using eutectic mixture of LiNO 3– LiOH – Li 2O 2. J. Power Sources 195 (2010) 4297 – 4303).
Summary of the invention
The object of the present invention is to provide that a kind of particle is tiny, particle diameter is evenly distributed, pattern is regular, under the high power charging-discharging condition, have relatively high specific capacity and the Li of cyclical stability 4Ti 5O 12-TiO 2/ C composite cathode material for lithium ion cell.
A kind of preparation method of composite cathode material for lithium ion cell is characterized in that: it is by Li 4Ti 5O 12, TiO 2, three kinds of components of C consist of.
Its concrete steps are:
(1) configuration solution: the pure butyl titanate of Analysis about Selection mixes with organic solvent as the titanium source, stirs, and makes clear solution, and wherein the addition of titanium is at 0.0001 ~ 0.1 mol/100 ml solvent;
The pure lithium acetate of Analysis about Selection is prepared according to atomic ratio Li/Ti=0.8 ~ 1.6 as the lithium source, and it is joined in settled solution, stirs;
The pure ammoniacal liquor of Analysis about Selection (quality percentage composition 25 ~ 28%) dropwise joins in solution as pH value conditioning agent, and wherein the addition of ammoniacal liquor is at 1 ~ 8 ml/100 ml solvent;
(2) mentioned solution is placed in autoclave, carries out solvent thermal reaction, synthesis condition is: 140 ~ 180 oC insulation 12 ~ 48 hours;
(3) with the product of step (2) gained with absolute ethanol washing, filter after, be placed in baking oven 80 ~ 120 oThe C oven dry obtains Li 4Ti 5O 12-TiO 2Presoma;
(4) under air atmosphere, the presoma of step (3) gained is warming up to 450 ~ 650 oC insulation 1.5 ~ 4 hours cools to room temperature with the furnace and makes Li 4Ti 5O 12-TiO 2Powder;
(5) Li that step (4) is made 4Ti 5O 12-TiO 2Mix in solvent with carbon source, be stirred to evenly, by rotary evaporation, carbon source evenly is coated on Li 4Ti 5O 12-TiO 2Particle surface;
(6) under the inertia protective atmosphere, the powder of step (5) gained is warming up to 550 ~ 650 oThen C insulation 1 ~ 5 hour cools to room temperature with the furnace, makes Li 4Ti 5O 12-TiO 2/ C composite negative pole material.
The described organic solvent of step (1) is unary alcohol, and described ammoniacal liquor is disposable joining in solution fast, also can slowly dropwise join in solution.
The described carbon source of step (5) is one or more in sucrose, glucose, starch, epoxy resin, fructose, PVdF.
The described inertia protective atmosphere of step (6) is one or both in nitrogen, argon gas.
TiO 2At Li 4Ti 5O 12-TiO 2Quality percentage composition in powder is that 5 ~ 50%, C is at Li 4Ti 5O 12-TiO 2Quality percentage composition in/C composite negative pole material is 1 ~ 10%, and carbon source does not enter basis material Li 4Ti 5O 12-TiO 2Lattice.
TiO 2At Li 4Ti 5O 12-TiO 2Content in powder is preferably 15 ~ 40%, if this is because TiO 2Content is too low, synthetic Li 4Ti 5O 12-TiO 2Grain diameter is larger, and is not obvious to the improvement of material ionic conductivity; TiO 2Too high levels, synthetic Li 4Ti 5O 12-TiO 2The too small easy reunion of particle is unfavorable for improving the chemical property of material.
Take into account consideration from capacity and conductivity, C is at Li 4Ti 5O 12-TiO 2Content in/C composite negative pole material is preferably 2 ~ 4%, if this is because carbon content is too low, can't fundamentally improve the electron conduction of material, and carbon content is too high, can reduce the specific capacity of material.
Li 4Ti 5O 12Material has good cyclical stability as " zero strain material "; TiO 2But the material removal lithium embedded, and when heat treatment, due to space steric effect, suppressed Li 4Ti 5O 12The growth of particle obtains nanometer Li 4Ti 5O 12-TiO 2Particle has shortened the lithium ion the evolving path, has improved the ionic conductivity of material; Carbon is dispersed between particle or is coated on particle surface, has good bridging action, improved material electron conduction, bringing into play three's advantage separately.
Adopt the negative material of this method preparation to have the following advantages:
(1) particle is tiny, and particle diameter is evenly distributed, and pattern is regular;
(2) carbon source does not enter basis material Li 4Ti 5O 12-TiO 2Lattice, be conducive to keep the structural stability of material;
(3) under the high power charging-discharging condition, have relatively high specific capacity and cyclical stability;
(4) each component can be brought into play advantage separately.
The present invention utilizes space steric effect, original position synthesis of nano Li by solvent-thermal method 4Ti 5O 12-TiO 2Composite material, and utilize rotary evaporation technique evenly to coat one deck carbon at particle surface, preparation Li 4Ti 5O 12-TiO 2/ C composite negative pole material.TiO 2Existence, capacity is provided on the one hand, stop particle to be grown up on the one hand, realize the nanometer of active powder; The nano active particle has good ionic conductivity; After coating, improves in carbon the electron conduction of material.The three is bringing into play advantage separately.Under the high current charge-discharge condition, Li 4Ti 5O 12-TiO 2/ C material have height ratio capacity, high cyclical stability and a high security, be a kind of well behaved lithium ion battery negative material.
The invention has the advantages that in the building-up process of material, flexible operation, simple, reaction condition is gentle, and phase formation, particle size and particle shape are easy to control.
Li 4Ti 5O 12-TiO 2/ C composite material is a kind of well behaved composite cathode material for lithium ion cell, and this material and preparation method thereof there is not yet document and patent report.
Description of drawings
Fig. 1 is the Li of embodiment 1 4Ti 5O 12-TiO 2The charging and discharging curve figure of/C.
Embodiment
The present invention will be further described below in conjunction with embodiment, but be not limited to protection scope of the present invention:
Embodiment 1:
Take the 2.383 g pure butyl titanates of analysis (purity 〉=99.0%) and be dissolved in 50 ml absolute ethyl alcohols, stir, make clear solution; According to atomic ratio Li/Ti=1.4, take 1.000 g lithium acetates (purity 〉=99.0%), join in settled solution, continue to stir until form homogeneous solution; Dropwise add 2 ml ammoniacal liquor to solution, mixed liquor is transferred in 100 ml autoclaves after mixing, and is placed in baking oven, 180 oC insulation 24 hours is cooled to room temperature, after the product of gained absolute ethanol washing, filtration, is placed in baking oven 80 oThe C oven dry obtains Li 4Ti 5O 12-TiO 2Presoma; Under air atmosphere, the presoma of gained is warming up to 600 oC insulation 2 hours cools to room temperature with the furnace and makes Li 4Ti 5O 12-TiO 2Powder, wherein, TiO 2At Li 4Ti 5O 12-TiO 2Content in powder is about 23%; Take 0.450 g Li 4Ti 5O 12-TiO 2Powder, 0.027 g sucrose mix both in absolute ethyl alcohol, be stirred to evenly, and by rotary evaporation, carbon source evenly is coated on Li 4Ti 5O 12-TiO 2Particle surface; Under the high pure nitrogen protective atmosphere, powder is warming up to 600 oThen C insulation 1 hour cools to room temperature with the furnace, makes Li 4Ti 5O 12-TiO 2/ C composite negative pole material, C is at Li 4Ti 5O 12-TiO 2Content in/C composite negative pole material is about 2%.
With the Li that makes 4Ti 5O 12-TiO 2The PVdF of the acetylene black of/C composite negative pole material, 10 wt%, 5 wt% mixes, and makes slurry, evenly is coated on Copper Foil, is stamped into the circular electrode pole piece after vacuum drying, take lithium metal as to electrode, and 1 mol/L LiPF 6/ EMC+DC+EC(volume ratio is 1:1:1) be electrolyte, Celgard 2400 is barrier film, forms test cell.Battery is carried out the constant current charge-discharge test, and current density is 5 C(1 C=175 mA/g), the charging/discharging voltage scope is 1.0 ~ 2.5 V.Result shows, its maximum reversible specific capacity reaches 167.7 mAh/g, and after 100 circulations, specific capacity remains on 150 mAh/g left and right.
Embodiment 2:
Take the 2.383 g pure butyl titanates of analysis (purity 〉=99.0%) and be dissolved in 50 ml absolute ethyl alcohols, stir, make clear solution; According to atomic ratio Li/Ti=1.4, take 1.000 g lithium acetates (purity 〉=99.0%), join in settled solution, continue to stir until form homogeneous solution; Dropwise add 1 ml ammoniacal liquor to solution, mixed liquor is transferred in 100 ml autoclaves after mixing, and is placed in baking oven, 180 oC insulation 24 hours is cooled to room temperature, after the product of gained absolute ethanol washing, filtration, is placed in baking oven 80 oThe C oven dry obtains Li 4Ti 5O 12-TiO 2Presoma; Under air atmosphere, the presoma of gained is warming up to 600 oC insulation 2 hours cools to room temperature with the furnace and makes Li 4Ti 5O 12-TiO 2Powder, wherein, TiO 2At Li 4Ti 5O 12-TiO 2Content in powder is about 19%; Take 0.450 g Li 4Ti 5O 12-TiO 2Powder, 0.026 g starch mix both in absolute ethyl alcohol, be stirred to evenly, and by rotary evaporation, carbon source evenly is coated on Li 4Ti 5O 12-TiO 2Particle surface; Under the high pure nitrogen protective atmosphere, powder is warming up to 600 oThen C insulation 1 hour cools to room temperature with the furnace, makes Li 4Ti 5O 12-TiO 2/ C composite negative pole material, C is at Li 4Ti 5O 12-TiO 2Content in/C composite negative pole material is about 2%.
Electrochemical property test is identical with embodiment 1.Result shows, its maximum reversible specific capacity reaches 165.5 mAh/g, and after 100 circulations, Capacitance reserve is in 150 mAh/g left and right.
Embodiment 3:
Take the 2.383 g pure butyl titanates of analysis (purity 〉=99.0%) and be dissolved in 50 ml absolute ethyl alcohols, stir, make clear solution; According to atomic ratio Li/Ti=1.2, take 0.857 g lithium acetate (purity 〉=99.0%), join in settled solution, continue to stir until form homogeneous solution; Dropwise add 2 ml ammoniacal liquor to solution, mixed liquor is transferred in 100 ml autoclaves after mixing, and is placed in baking oven, 180 oC insulation 24 hours is cooled to room temperature, after the product of gained absolute ethanol washing, filtration, is placed in baking oven 80 oThe C oven dry obtains Li 4Ti 5O 12-TiO 2Presoma; Under air atmosphere, the presoma of gained is warming up to 600 oC insulation 2 hours cools to room temperature with the furnace and makes Li 4Ti 5O 12-TiO 2Powder, wherein, TiO 2At Li 4Ti 5O 12-TiO 2Content in powder is about 25%; Take 0.450 g Li 4Ti 5O 12-TiO 2Powder, 0.044 g glucose mix both in absolute ethyl alcohol, be stirred to evenly, and by rotary evaporation, carbon source evenly is coated on Li 4Ti 5O 12-TiO 2Particle surface; Under the high pure nitrogen protective atmosphere, powder is warming up to 600 oThen C insulation 1 hour cools to room temperature with the furnace, makes Li 4Ti 5O 12-TiO 2/ C composite negative pole material, C is at Li 4Ti 5O 12-TiO 2Content in/C composite negative pole material is about 2%.
Electrochemical property test is identical with embodiment 1.Result shows, its maximum reversible specific capacity reaches 131.4 mAh/g, and after 100 circulations, Capacitance reserve is in 115 mAh/g left and right.

Claims (6)

1. the preparation method of a composite cathode material for lithium ion cell, it is characterized in that: it is by Li 4Ti 5O 12, TiO 2, three kinds of components of C consist of, processing step is:
(1) configuration solution: the pure butyl titanate of Analysis about Selection mixes with organic solvent as the titanium source, stirs, and makes clear solution, and wherein the addition of titanium is at 0.0001 ~ 0.1 mol/100 ml solvent;
The pure lithium acetate of Analysis about Selection is prepared according to atomic ratio Li/Ti=0.8 ~ 1.6 as the lithium source, and it is joined in clear solution, stirs;
Select the pure ammoniacal liquor of analysis of weight percentage 25 ~ 28% as pH value conditioning agent, dropwise join in solution, wherein the addition of ammoniacal liquor is at 1 ~ 8 ml/100 ml solvent; Wherein, described organic solvent is unary alcohol;
(2) mentioned solution is placed in autoclave, carries out solvent thermal reaction, synthesis condition is: 140 ~ 180 ℃ are incubated 12 ~ 48 hours;
(3) with the product of step (2) gained with absolute ethanol washing, filter after, be placed in 80 ~ 120 ℃ of oven dry of baking oven, obtain Li 4Ti 5O 12-TiO 2Presoma;
(4) under air atmosphere, the presoma of step (3) gained is warming up to 450 ~ 650 ℃ of insulations 1.5 ~ 4 hours, cools to room temperature with the furnace and make Li 4Ti 5O 12-TiO 2Powder;
(5) Li that step (4) is made 4Ti 5O 12-TiO 2Mix in solvent with carbon source, be stirred to evenly, by rotary evaporation, carbon source evenly is coated on Li 4Ti 5O 12-TiO 2Particle surface;
(6) under the inertia protective atmosphere, the powder of step (5) gained is warming up to 550 ~ 650 ℃ of insulations 1 ~ 5 hour, then cool to room temperature with the furnace, make Li 4Ti 5O 12-TiO 2/ C composite negative pole material.
2. the preparation method of composite cathode material for lithium ion cell according to claim 1, it is characterized in that: the described carbon source of step (5) is one or more in sucrose, glucose, starch, epoxy resin, fructose, PVdF.
3. the preparation method of composite cathode material for lithium ion cell according to claim 1, it is characterized in that: the described inertia protective atmosphere of step (6) is one or both in nitrogen, argon gas.
4. the preparation method of composite cathode material for lithium ion cell according to claim 1, is characterized in that: TiO 2At Li 4Ti 5O 12-TiO 2Quality percentage composition in powder is that 5 ~ 50%, C is at Li 4Ti 5O 12-TiO 2Quality percentage composition in/C composite negative pole material is 1 ~ 10%, and carbon source does not enter basis material Li 4Ti 5O 12-TiO 2Lattice.
5. the preparation method of composite cathode material for lithium ion cell according to claim 4, is characterized in that: TiO 2At Li 4Ti 5O 12-TiO 2Quality percentage composition in powder is 15 ~ 40%.
6. the preparation method of composite cathode material for lithium ion cell according to claim 4, it is characterized in that: C is at Li 4Ti 5O 12-TiO 2Quality percentage composition in/C composite negative pole material is 2 ~ 4%.
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溶胶_凝胶法制备Li4Ti5O12/C复合负极材料及性能研究;单宇 等;《电源技术》;20101231;第34卷(第12期);1236-1238 *

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